Showing papers by "Glenn M. Sammis published in 2014"
TL;DR: The first example of a photoredox catalytic method for the formation of carbon-fluorine (C-F) bonds is developed, and the mild reaction conditions and use of visible light make it a practical improvement over previously developed UV-mediated decarboxylative fluorinations.
Abstract: We have developed the first example of a photoredox catalytic method for the formation of carbon–fluorine (C–F) bonds. The mechanism has been studied using transient absorption spectroscopy and involves a key single-electron transfer from the 3MLCT (triplet metal-to-ligand charge transfer) state of Ru(bpy)32+ to Selectfluor. Not only does this represent a new reaction for photoredox catalysis, but the mild reaction conditions and use of visible light also make it a practical improvement over previously developed UV-mediated decarboxylative fluorinations.
176 citations
TL;DR: Mechanical investigations suggest that the cascade reaction proceeds through a cyclic diazene intermediate prior to the cycloreversion of bromoallyl hydrazones.
Abstract: The highly efficient and diastereoselective synthesis of E dienes has been accomplished through radical cyclization of bromoallyl hydrazones. This methodology has been further extended to generate these products through a one-pot condensation/radical cyclization/cycloreversion cascade from simple aldehyde starting materials in high yields (>75 %) and high diastereoselectivities (>95:5). Mechanistic investigations suggest that the cascade reaction proceeds through a cyclic diazene intermediate prior to the cycloreversion.
19 citations
TL;DR: In this article, the direct formation of C-F bonds by photodecarboxylation of aryloxyacetic acid derivatives is developed. But this method is not suitable for the use of synthetic derivatives.
Abstract: The direct formation of C—F bonds by photodecarboxylation of aryloxyacetic acid derivatives is developed.
6 citations
TL;DR: In this article, the highly efficient and diastereoselective synthesis of Edenes has been accomplished through radical cyclization of bromoallyl hydrazones, which has been further extended to generate these products through a one-pot condensation/radical cyclization/cycloreversion cascade from simple aldehyde starting materials.
Abstract: The highly efficient and diastereoselective synthesis of E dienes has been accomplished through radical cyclization of bromoallyl hydrazones. This methodology has been further extended to generate these products through a one-pot condensation/radical cyclization/cycloreversion cascade from simple aldehyde starting materials in high yields (>75 %) and high diastereoselectivities (>95:5). Mechanistic investigations suggest that the cascade reaction proceeds through a cyclic diazene intermediate prior to the cycloreversion.
3 citations